CN102187022A - Article formed from electrospinning a dispersion - Google Patents

Article formed from electrospinning a dispersion Download PDF

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Publication number
CN102187022A
CN102187022A CN2009801405233A CN200980140523A CN102187022A CN 102187022 A CN102187022 A CN 102187022A CN 2009801405233 A CN2009801405233 A CN 2009801405233A CN 200980140523 A CN200980140523 A CN 200980140523A CN 102187022 A CN102187022 A CN 102187022A
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Prior art keywords
dispersion
compound
goods
curable
liquid
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CN2009801405233A
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CN102187022B (en
Inventor
R·M·希尔
E·J·乔夫里
D·T·莱尔斯
B·J·路德维格
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Dow Silicones Corp
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Dow Corning Corp
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D01D5/0038—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion the fibre formed by solvent evaporation, i.e. dry electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/38—Formation of filaments, threads, or the like during polymerisation
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/62—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyesters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
    • Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
    • Y10T442/681—Spun-bonded nonwoven fabric

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Nonwoven Fabrics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

An article of fibers includes a cured compound. The fibers are formed from electrospinning a dispersion. The dispersion includes a liquid and a condensation curable compound. A content of the liquid in the dispersion is reduced such that the condensation curable compound cures. The article is formed from a method of manufacturing which includes the step of forming the dispersion. The method also includes the step of electro spinning the dispersion to reduce the content of the liquid such that the condensation curable compound cures.

Description

The goods that form by the electrostatic spinning dispersion
Invention field
The method of relate generally to goods of the present invention and these goods of manufacturing.More specifically, this method comprises the dispersion that forms the compound that contains liquid and condensation curable, and this dispersion of electrostatic spinning, makes goods.
The explanation of related art
The fiber that exploitation has micron and nanometer diameter is the focus of a large amount of research and development of industry, academia and government at present.Can be by organic and inorganic material, polyaniline for example, polypyrrole, Polyvinylidene, polyacrylonitrile, polyvinyl chloride, polymethyl methacrylate, the polyacetylene that polythiophene and iodine mix forms the fiber of these types.Except polyethylene and synthesis hydrophilic polymer, for example beyond the poly(ethylene oxide), also by hydrophilic biopolymer, protein for example, polysaccharide, collagen, fibrinogen, silk and hyaluronic acid form this fibrid.
Can form the fiber of many these types by the method that this area is called electrostatic spinning.Electrostatic spinning is to comprise the universal method of using electrostatic charge to form fiber mat.Typically, electrostatic spinning comprises solution loaded in the syringe, and drives the tip of this solution to syringe with syringe pump, forms drop at the tip.Electrostatic spinning also generally includes and applies voltage to pin, forms the charged jet of solution.Extend jet then, and twist thread continuously, be deposited on the ground connection gatherer, thereby form fiber mat up to it by Coulomb repulsion.
Can be in wide in range various industry, comprising in medical science and science application, using the fiber that forms by electrostatic spinning.More specifically, used this fibrid to strengthen some composites.The nanotube that has also used these fiber production in medical science dialysis, gas separation, infiltration and water treatment, to use.
In some applications, by all kinds of two-phases of electrostatic spinning and three-phase system emulsion for example, form fiber.The electrostatic spinning technique that uses with these systems typically produces the fiber that demonstrates the non-required mechanical features of giving fiber weakness and brittleness.Therefore, still need form and demonstrate the fibre of improved stress and strain performance by dispersion.Still need to develop the method that forms this goods.
Summary of the invention and advantage
The invention provides the method for goods and these goods of manufacturing of fiber.Fiber comprises the compound of curing and is formed by the electrostatic spinning dispersion.This dispersion comprises liquid and curable compound.This method comprises the step that forms dispersion and this dispersion of electrostatic spinning.In one embodiment, this method comprises the step of the compound of cure curable.
The electrostatic spinning dispersion allows to form the fiber that demonstrates the compound characteristic feature of curing and demonstrate improved stress and strain performance.Form this fiber and allow more effectively and accurately to produce the various materials that in medical science, science and process industry, use.Using this dispersion also to allow to use the compound of all kinds of condensation curables to form can be based on required physics and the treatable product of chemical.
The accompanying drawing summary
To easily understand other advantages of the present invention, because when taking into consideration,, will understand these advantages better by with reference to following detailed description with accompanying drawing, wherein Fig. 1 is the scanning electron microscope image that contains the goods of fiber of the present invention, and described fiber comprises fiber-fiber contact and ball defects.
Detailed Description Of The Invention
The invention provides article comprising fibers (being fibre), as shown in Figure 1.The present invention also provides the method for making goods.This method comprises the step of electrostatic spinning, as described in more detail below.
Goods can comprise single layer fibre or multi-layer fiber.Just because of this, the thickness of goods can be at least 0.01 micron.More typically, the thickness of goods be about 1 micron-Yue 100 microns and the most typically thickness be about 25 microns-Yue 100 microns.Goods are not limited to the fiber number of plies of any given number.Goods can be weaved or be non-woven, and can demonstrate microphase-separated.In one embodiment, the woven and goods of fiber and goods right and wrong are further defined as mat.In another embodiment, fiber and goods right and wrong are woven, and goods are further defined as net.Perhaps, goods can be films.Fiber also can be even or uneven and can have any surface roughness.Goods can waterproof, and are water-fast, fire-retardant, conduction, and automatically cleaning, draining, sagging reduces, and combination.In one embodiment, goods are coatings.Think that also goods can be fabrics, breathable fabric, filter, or its combination.In addition, can be in various industry, for example at catalyst, filter, solar cell, electronic building brick, these goods of use in skin patch, bandage, drug delivery system and in antimicrobial application.The potential application of another of goods can be as super hydrophobic perforated membrane in order to oil-moisture from or at biomedical devices, for example use and in burn bandage, use in the blood vessel substitute, but so that NA respiratory to be provided.
Goods can be super hydrophobic fibers, and can demonstrate the water contact angle greater than about 150 degree.In various embodiments, goods demonstrate 150-180,155-175, the water contact angle of 160-170 and 160-165 degree.Goods also can demonstrate the water contact angle that is lower than 15 degree and lag behind.In various embodiments, goods demonstrate 0-15,5-10, and the water contact angle of 8-13 and 6-12 lags behind.Goods also can demonstrate isotropism or the non-isotropic character that water contact angle and/or water contact angle lag behind.Perhaps, goods can comprise zone that demonstrates isotropic nature and the zone that demonstrates non-isotropy character.
Fiber can have any size and dimension, and typically is cylindrical.Typically, the diameter of fiber is 0.01-100, more typically 0.05-10 and the most typically 0.1-1 micron.In various embodiments, the diameter of fiber is 1 nanometer-30 micron, the 1-500 nanometer, the 1-100 nanometer, 100-300 nanometer, 100-500 nanometer, the 50-400 nanometer, 300-600 nanometer, 400-700 nanometer, the 500-800 nanometer, the 500-1000 nanometer, 1500-3000 nanometer, 1000-5000 nanometer, 2000-5000 nanometer, or 3000-4000 nanometer.Fiber also typically has the size of 5-20 micron and more typically has the size of 10-15 micron.Yet fiber is not limited to any specific size.Fiber usually is called " fine fibre ", and it comprises the fiber (being the fiber of at least 1 micron of diameter) with micron order diameter and the fiber with nanometer grade diameter (be diameter less than 1 micron fiber).Glass transition temperature (the T of this fiber g) also can be 25 ℃-500 ℃.
Also can pass through any way known in the art, fiber is connected to each other go up.For example, fiber can be therein their overlap or the place that can physically separate fuses together so that fiber only is laid on each other and goes up in goods.Think that fiber when connecting, can form net or pad that cell size is the 0.01-100 micron.In various embodiments, the cell size range size is 0.1-100,0.1-50,0.1-10,0.1-5,0.1-2 or 0.1-1.5 micron.Be appreciated that cell size can be even or inhomogeneous.That is to say that goods can be included in a certain zone or have the zones of different of different cell sizes between each zone.In addition, fiber can have any section feature, comprising but be not limited to the belt section feature, the elliptic cross-section feature, the circular cross-section feature, and the combination.In some embodiments, can be observed " becoming bead (beading) " of fiber, this uses for great majority is acceptable.The existence of bead, the diameter of cross section curve of fiber (changing to band shape from circle) and fiber are the functions that forms the condition of the method for fiber, as described further below.
In some embodiments, fiber is fireproof also, as mentioned above.The UL-94V-0 testing vertical flammability of use on the small pieces of the non-woven mat that deposits on the aluminum foil substrate, the fire line of test fiber, especially fibrous non-woven mat.In this test, the rectangular of non-woven mat remained on the flame top about 10 seconds.Remove flame then 10 seconds, and applied other 10 seconds again.The red-hot dropping of observation sample propagating flame in this technical process, residual flame and residual vehement existence, and along the ignition distance of the height of sample.For the non-woven mat that contains fiber of the present invention, below those fibers of burning, typically observe complete fiber.The non-woven mat imperfect combustion is the evidence from fire extinguishing, a kind of typical behavior of fire proofing and be regarded as good fire resistance.In many cases, non-woven mat can even be realized UL 94 V-0 grades.Be bound by under the situation of any particular theory not wishing, it is low with the ratio of silicon atom to think that fire resistance typically is attributable in the fiber organic group.The ratio of organic group and silicon atom is low to be attributable to not have organic polymer and organic copolymer in fiber.Yet, think that also fire resistance may be due to the ratio of organic group and silicon atom in the fiber factor low.
Can form fiber by dispersion.As known in the art, dispersion comprises another unmixing and a phase of a kind of material of dispersion, i.e. decentralized photo in continuous phase mutually within it with material.In the present invention, dispersion comprises liquid and curable compound, as described in more detail below.In one embodiment, liquid is nonpolar liquid.In another embodiment, liquid is polar liquid, and is for example pure, ionic liquid, or water.Typically, liquid is water.Water can be running water, well water, and purified water, deionized water, and combination, and can be present in the dispersion by various consumptions, this depends on the type of dispersion.Liquid can be decentralized photo or continuous phase.In one embodiment, dispersion comprises the solid particle of decentralized photo form and the liquid of continuous phase form.In another embodiment, dispersion comprise nonpolar liquid as decentralized photo and polar liquid as continuous phase.In various embodiments, the amount of liquid can be 20-80, and 30-70,40-60 or consumption are about 50 weight portions, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
Dispersion can be further defined as " colloid " or " aqueous colloidal dispersion ", and these two terms are used interchangeably.Typically, colloid is included in the particle of the size of dispersion in the continuous phase less than 100 nanometers.Colloid can be classified according to variety of way.For purpose of the present invention, colloid also can be categorized as gel (liquid dispersion phase and solid continuous phase), emulsion (liquid dispersion phase and liquid continuous phase), and/or foam (gas dispersion phase and liquid continuous phase).Colloid can turning (promptly to exist greater than a kind of state) or is not turning.In addition, colloid can be an elasticity or viscoelastic.
In one embodiment, dispersion is further defined as emulsion, at first introduces as above.According to disperseing and the chemical property of continuous phase, emulsion typically is categorized as a kind of in four classes.The first kind is oil-in-water (O/W) emulsion.The O/W emulsion typically is included in the nonpolar decentralized photo (for example, oil) in the water continuous phase (for example water) of containing that forms drop (described drop is typically called emulsion particle).For purpose of the present invention, term " oil " comprises nonpolar molecule and can comprise curable compound.Second kind of emulsion is Water-In-Oil (W/O) emulsion.The W/O emulsion typically is included in the polarity decentralized photo in the nonpolar continuous phase, thereby forms the upset emulsion.The 3rd class is W/O/W (W/O/W) emulsion.The emulsion of these types is included in the polarity decentralized photo in the nonpolar continuous phase, and described nonpolar continuous phase itself is dispersed in again in the polarity continuous phase.For example, the W/O/W emulsion can comprise the water droplet that is captured in than in the larger oil droplet, describedly is dispersed in again in the continuous water than larger oil droplet itself.The 4th class is water Bao Shui (W/W) emulsion.The emulsion of these types is included in the aqueous solvent chemoattractant molecule in the continuous aqueous solution, and wherein the aqueous solvent chemoattractant molecule comprises water-soluble different molecule with the continuous aqueous solution.Be bound by under the situation of any particular theory not planning, thinking that the emulsion of aforementioned type depends on disperses and the two hydrogen bonding of continuous phase pi accumulation, and/or salt bridging.In the present invention, dispersion can be further defined as any in this four classes emulsion.
This area is also known, to a certain extent, and the dispersion instability.Typically, there are three class dispersion unstability, flocculate comprising (i), wherein the particle of decentralized photo forms agglomerate in continuous phase, (ii) creaming, wherein the particle of decentralized photo towards the surface of continuous phase or the bottom concentrate and (iii) breakdown of emulsion and coalescent, the wherein particles coalesce of decentralized photo and in continuous phase, form liquid level.Dispersion of the present invention can demonstrate the unstability of one or more these types.
Dispersion of the present invention can comprise the particle of change in size.In one embodiment, dispersion comprises the particle of 1 nanometer-10 micron, more typically 1 nanometer-1 micron and the most typically 1-100 nanometer.In another embodiment, dispersion can be categorized as nanoemulsions.Dispersion can comprise the particle little or bigger than above-described size, and this depends on those skilled in the art's demand.
As mentioned above, dispersion also comprises curable compound.Curable compound can be curable any organic or inorganic compound known in the art.The non-limiting example of suitable curable compound comprises the compound by free radical mechanism, hydrosilylation, condensation, addition reaction, ultraviolet light, microwave and heat cure.This curable examples for compounds includes but not limited to peroxide, acid amides, and acrylate, ester, ether, acid imide, oxirane, sulfone, urea, carbamate has the compound of ethylenic unsaturated bond, and makes up.In one embodiment, curable compound is selected from silane, siloxanes, silazane, silicone, silica, silene (silenes), silsesquioxane, and combination.In this embodiment, curable compound typically solidifies by free radical, condensation and/or hydrosilylation mechanism.In various embodiments, the amount of curable compound can be 20-80,30-70, and 40-60, or consumption is about 50 weight portions, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
Perhaps, curable compound can be further defined as the compound of condensation curable.As known in the art, the compound of condensation curable solidifies by condensation reaction.Condensation reaction be wherein two molecules in conjunction with forming new single molecule and losing for example chemical reaction of water of micromolecule.When losing water, condensation reaction also can be described as dehydration.Just to purpose of description, below listed general condensation (dehydration) reacting flow chart:
Figure BDA0000055051390000061
Wherein R is the organic or inorganic part.Condensation reaction is not limited to lose water, also can comprise losing organic or inorganic compound or hydrogen molecule.Under the situation that one or more silicon atoms in the reacting flow chart are substituted by carbon (C) atom, also condensation reaction can take place therein.
The compound of condensation curable can comprise monomer, dimer, oligomer, polymer, prepolymer, copolymer, block polymer, star polymer, graft polymers, random copolymer, macromonomer, telechelic oligoner, nano particle, and combination.Term as used herein " oligomer " comprises the reactive appraisable chemical group that partly links together by the energy condensation, comprising dimer, and tripolymer, the tetramer and/or pentamer.The example that can be included in the preferred organic reaction part that can condensation in the compound of condensation curable includes but not limited to hydrolyzable part, hydroxylic moiety, hydride, isocyanate moiety, amine moiety, amide moieties, acid moieties, alcohol moiety, amine moiety, acrylate part, carbonate moiety, epoxide moiety, ester moiety, and combination.The compound of condensation curable also can comprise inorganic part, comprising but be not limited to silicone, siloxanes, silane, transistion metal compound, and the combination.Except condensation reaction, goods of the present invention also can be by various addition reactions, free radical addition for example, and the Miachael addition, hydrosilylation reactions, and/or Diels Alder reaction forms.Also can adopt ring-opening polymerization.
In one embodiment, the compound of condensation curable can be any compound in 11/20/07 U.S. Provisional Application of submitting to number 61/003726, at this specially by with reference to introducing.In another embodiment, the compound of condensation curable can comprise organic and inorganic polymer, polyester for example, polyamide, polyimides, polyureas, polyethers, polyamine, polyurethane, aramid, Merlon, carbonic acid ester, and combination.Perhaps, the curable formation of the compound of condensation curable is selected from the compound of polyester, nylon, polyurethane, aromatic polyamides, carbonic acid ester and combination thereof.
(condensation) curable compound can be substantially free of silicon (being the compound of silicon atom and/or silicon atoms).Be appreciated that term " be substantially free of " be meant silicon concentration less than 5000, more typically less than 900 with the most typically less than the compound of 100 parts of silicon atoms, with respect to the compound meter of 1,000,000 parts of condensation curables.Think that also (condensation) curable compound can be not siliceous fully.
Perhaps, (condensation) curable compound can comprise the polymerizate of at least a silicon monomer and organic monomer.Think that organic monomer and/or silicon monomer can be present in (condensation) curable compound with any volume fraction.In various embodiments, organic monomer and/or silicon monomer be with 0.05-0.9,0.1-0.6, and 0.3-0.5,0.4-0.9,0.1-0.9, the volume fraction of 0.3-0.6 or 0.05-0.9 exists.
Organic monomer can comprise above-described any organic moiety.Term " silicon monomer " comprises any monomer that contains at least one silicon (Si) atom, silane for example, siloxanes, silazane, silicone, silica, silene, silsesquioxane, and combination.Be appreciated that silicon monomer can comprise the group of polymerization and keep silicon monomer, as long as it keeps the ability of polymerization.In one embodiment, silicon monomer is selected from silane, silsesquioxane, siloxanes, and combination.
In can supplying the embodiment that substitutes, (condensation) curable compound is selected from organosilanes, organopolysiloxane, and combination.In this embodiment, organopolysiloxane can be selected from silanol stopped siloxanes, the siloxanes of alkoxysilyl end-blocking, and combination.
(condensation) curable compound can be straight chain or non-straight chain, and can comprise that hydroxyl and/or organic group siloxy are (SiOR), and can comprise hydroxy-end capped dimethyl silicone polymer.(condensation) curable compound can comprise following formula:
Figure BDA0000055051390000081
Each R wherein 1And R 2Comprise hydrogen independently, hydroxyl, alkyl, the alkyl that halogen replaces, alkenyl, aryl, the aryl that halogen replaces, alkaryl, alkoxyl, acyloxy, ketoxime base (ketoximate), amino, amide groups, sour amide groups, aminooxy group, in sulfydryl and the alkenyl oxy one and n can be any integers.
Perhaps, (condensation) curable compound can comprise alkylene and/or fluoro alkylene.Alkylene comprises the divalent moiety of carbon containing and hydrogen.The fluoro alkylene comprises the alkylene part that at least one hydrogen is replaced by at least one fluorine atom.Typical fluoro alkylene comprises the partially or completely alkylidene of fluorine replacement.(condensation) curable compound also can comprise the alkene part, comprising the acrylate part, and methacrylic acid ester moiety, vinyl segment, acetenyl part, and combination.
If (condensation) curable compound comprises hydroxyl, then (condensation) curable organic based polysiloxane can comprise having at least one terminal silanol or be bonded to hydrogen atom on the silicon or the type siloxane of hydrolyzable groups, and described hydrolyzable groups forms silanol group when being exposed to moisture following time.The silanol group that end or side are hung or its precursor allow condensation.
Perhaps, (condensation) curable compound can be further defined as elastomer or curable elastomer.Just as known in the art, " elastomer " is to demonstrate elasticity, can be out of shape and return to the roughly compound of original shape under stress.In the present invention, term " elastomer " is not limited to polymer or monomer, and can comprise a kind of or these two.In addition, elastomer can comprise any aforementioned (condensation) curable compound.In one embodiment, curable elastomer is available commercially from Dow CorningCorporation of Midland, MI with trade name Dow Corning 84 Additive.
In one embodiment, the number-average molecular weight (M of curable compound n) greater than 5000g/mol with more typically greater than 10,000g/mol.Yet curable compound is not limited to this number-average molecular weight.In another embodiment, the number-average molecular weight of curable compound is greater than about 100,000g/mol.In various other embodiments, the number-average molecular weight of curable compound is 100,000-5,000,000g/mol, 100,000-1,000,000g/mol, 100,000-500,000g/mol, 200,000-300,000g/mol, be higher than about 250,000g/mol, or about 150,000g/mol.In an embodiment again, the number-average molecular weight of curable compound is greater than 50,000g/mol and more typically greater than 100,000g/mol.In can be for the embodiment that substitutes, the number-average molecular weight of curable compound can be at least about 300g/mol, and is about 1, and 000-is about 2,000g/mol, or about 2, and 000g/mol-is about 2,000,000g/mol.In other embodiments, the number-average molecular weight of curable compound is greater than 350g/mol, and is about 5, and 000-is about 4,000,000g/mol, or about 500, and 000-is about 2,000,000g/mol.
Except curable compound, dispersion also can comprise one or more surfactants.In various embodiments, dispersion comprises (first) surfactant and second surface activating agent or kinds of surface activating agent.Before forming dispersion, surfactant can with liquid, with curable compound, or with liquid and curable compound the two combines.Typically, before forming dispersion, surfactant combines with liquid.Surfactant is also referred to as surface-active agents, surface-activity solute, emulsifying agent, emulgent, and interfacial agent.With respect to the present invention, term " surface-active agents ", " surface-activity solute ", " surfactant ", " emulsifying agent ", " emulgent " and " interfacial agent " is used interchangeably.Surfactant reduces the surface tension of liquid by in liquid-gas interface place absorption.Surfactant also by in the absorption of liquid-liquid interface place, reduces the interfacial tension between polarity and the nonpolar molecule.Be bound by under the situation of any particular theory not planning, think that surfactant works at the interface at these, and depend on various factors, comprising the excluded volume repulsive force, electrostatic interaction power, Van der Waals force, entropic force and steric hindrance power.In the present invention, can select or the control surface activating agent based on one or more these factors.
Surfactant, first and second surfactants, or the first/the second/can be independently selected from non-ionic surface active agent with the kinds of surface activating agent, cationic surfactant, anion surfactant, amphoteric surfactant, and combination.Suitable ionic surfactant pack is drawn together but is not limited to the alkylphenol alkoxide, and pure b-oxide is comprising aliphatic alcohol ethyl oxide, glyceride, Isosorbide Dinitrate, sucrose and glucose ester, comprising alkyl poly glucoside and hydroxyalkyl glycan glycosides, alkanolamide, N-alkyl glucose amide, the alkylene oxide block copolymer, for example oxirane, expoxy propane and/or epoxy butane block copolymer, polyhydroxy and many alkoxyls derivative of fatty acid, amine oxide, siloxy group polyethers, and combination.
Suitable cationic surfactants includes but not limited to the interfacial activity compound, and comprising ammonium, for example alkyl dimethyl ammonium halide and chemical formula are RR`R``R```N +X -Compound, wherein R, R`, R`` and R``` be independently selected from alkyl, aryl, alkyl alkoxy, alkoxy aryl, hydroxyalkyl (alkoxyl) and hydroxyaryl (alkoxyl) and wherein X be anion.Suitable anion surfactant includes but not limited to aliphatic alcohol sulfate.The further non-limiting example of suitable anion surfactant comprises alkyl sulfonate, linear alkylbenzene sulfonate (LAS) and straight chained alkyl toluene fulfonate.Again further; anion surfactant can comprise alkene sulfonate and disulfonate, the mixture of olefine and hydroxyl alkane-sulfonate or disulfonate, alkyl ester sulfonate; the sulfonation polycarboxylic acids; alkyl glycerol sulfonate, fatty acid glyceride sulfonate, alkyl phenol polyglycol ether sulfate; alkene sulfonate; alkane sulfonate, alkylphosphonic, the different thiosulfate of acyl group; acyl taurine salt; acyl methyl taurine salt, alkyl succinic acid, sulfosuccinate; alkenyl succinic and corresponding ester and acid amides; alkyl sulfosuccinic acid and corresponding amide, the monoesters of sulfosuccinic acid and diester, acyl sarcosinates; the sulphation alkyl poly glucoside; alkyl polyglycols carboxylic acid ester, hydroxyalkyl sarcosinate, and combination.Suitable amphoteric surfactant includes but not limited to contain the second month in a season of anionic group and/or the aliphatic derivatives of tertiary amine, betaine, and combination.
In addition, the surfactant and/or first and second surfactants can comprise aliphatic series and/or aromatics alkoxylated alcohols independently, LAS (linear alkylbenzene sulfonate (LAS)), alkane sulfonate, FAS (aliphatic alcohol sulfate), FAES (fatty alcohol ether sulphate), aklylene glycol, the trimethylolpropane b-oxide, the glycerine b-oxide, pentaerythrite b-oxide, the alkoxide of bisphenol-A, with the alkoxide of 4-methyl cyclohexanol and 5-methyl-2-propyl enanthol, and combination.Typically, the amount of surfactant is with respect to 100 weight portion dispersion meter 0.1-100 weight portions, 0.01-5 weight portion more typically, even more typically 0.5-5 weight portion and the most typically 1.5-5 weight portion.
Dispersion also can comprise thickener.As known in the art, thickener increases the viscosity of dispersion under low shearing speed, keeps the mobile performance of dispersion simultaneously under higher shear rate.The suitable thickening of Shi Yonging includes but not limited to polyalkylene oxide in the present invention, poly(ethylene oxide) for example, poly(propylene oxide), polybutylene oxide, and combination.In one embodiment, thickener is selected from alginic acid and derivative thereof, poly(ethylene oxide), polyvinyl alcohol, methylcellulose, hydroxypropyl methylcellulose, alkyl and hydroxy alkyl cellulose, carboxymethyl cellulose, hydroxyethylcellulose, guar gum, Arabic gum, ghatti gum, polyvinylpyrrolidone, starch, modified starch, tamarind gum, xanthans, polyacrylamide, polyacrylic acid, and combination.Thickener also can comprise nano particle, for example titanium dioxide and/or nanoclay, for example bentonite.Thickener also can be conduct electricity, partly lead, insulation, magnetic or luminous.Perhaps, thickener can comprise conducting polymer, polypyrrole for example, polyaniline, and/or polyacetylene.Thickener also can comprise biological components, for example protein or DNA.
Before forming dispersion, can be in conjunction with thickener and liquid, with curable compound, or with liquid and curable compound these two.Typically, before forming dispersion, in conjunction with thickener and liquid.The amount of thickener typically is 0.001-25, and more typically 0.05-5 and the most typically 0.1-5 weight portion are with respect to 100 weight portion dispersion meters.
This area is also known, and dispersion typically has two kinds of dissimilar viscosity, the viscosity of total viscosity and decentralized photo.The total viscosity of dispersion of the present invention under 25 ℃ temperature typically is at least 20 centistokes.In various embodiments, use is furnished with hot pond and the Brookfield rotating disc viscosimeter of the SC4-31 spindle operated under the rotary speed of 25 ℃ constant temperature and 5rpm, under 25 ℃ temperature, the viscosity of dispersion is at least 20 centistokes, about 100 centistokes of more typically about 30-, about 75 centistokes of the most about 40-.Do not limit the viscosity of decentralized photo, and think that it does not influence total viscosity.In one embodiment, decentralized photo is solid and has unlimited viscosity.
The zero shear rate viscosity of this dispersion also can be 0.1-10,0.5-10,1-10,5-8, or about 6PaS.In addition, the conductivity of dispersion can be 0.01-25mS/m.In various embodiments, the conductivity scope of dispersion is 0.1-10mS/m, 0.1-5mS/m, 0.1-1mS/m, 0.1-0.5mS/m, or about 0.3mS/m.The surface tension of this dispersion also can be 10-100mN/m.In different embodiments, the surface tension scope is 20-80mN/m, or 20-50mN/m.In one embodiment, the surface tension of dispersion is about 30mN/m.The dielectric constant of this dispersion also can be 1-100.In various embodiments, dielectric constant is 5-50,10-70, or 1-20.In one embodiment, the dielectric constant of dispersion is about 10.
Dispersion also can comprise additive.Additive can include but not limited to that conductivity improves additive, salt, dyestuff, colouring agent, labelled reagent, and combination.Conductivity improves additive and can help fiber with excellent formation and can make that further fibre diameter minimizes, particularly when forming fiber by electrostatic spinning.In one embodiment, conductivity raising additive comprises ionic compound.In another embodiment, conductivity improves additive and is selected from amine usually, organic salt and inorganic salts, and composition thereof.Typical conductivity improves additive and comprises amine, quaternary ammonium salt, quaternary alkylphosphonium salt, uncle's sulfonium salt, and the mixture of inorganic salts and organic ligand.More typical conductivity improves additive and comprises quaternary ammonium group organic salt, comprising but be not limited to tetrabutylammonium chloride, TBAB, tetrabutylammonium iodide, the phenyl trimethyl ammonium chloride, phenyl triethyl ammonium chloride, phenyl trimethylammonium bromide, phenyl trimethyl ammonium iodide, Dodecyl trimethyl ammonium chloride, DTAB, dodecyl trimethyl ammonium iodide, tetradecyl trimethyl ammonium chloride, Tetradecyl Trimethyl Ammonium Bromide, myristyl trimethyl ammonium iodide, hexadecyltrimethylammonium chloride, softex kw and cetyl trimethyl ammonium iodide.Additive can be present in the continuous phase or decentralized photo of dispersion with any consumption that those skilled in the art select, as long as the consumption of additive allows curable compound to take place to solidify.In various embodiments, it is about 25% that the consumption of additive typically is about 0.0001-, and more typically about 0.001-about 10% and more typically about 0.01-are about 1%, based on the gross weight of fiber.In one embodiment, additive comprises the methyl aminomethyl propanol.
The method of making goods now is discussed, and this method comprises the step that forms dispersion as mentioned above.Can form dispersion by adding curable compound and liquid together and mixing.In one embodiment, this method comprises the compound that adds condensation curable together and liquid and the step of mixing.Blend step can comprise the use ribbon blender, plough formula mixer, and the fluidisation blade-paddle mixer, ∑ (sigma) blade mixer, the rotary drum mixing machine, the eddy current mixer, the raw material mixer, vertical mixer, horizontal mixer, the rotor-stator mixer, ultrasonic device,
Figure BDA0000055051390000131
And the combination mechanical mixture of carrying out.
The invention is not restricted to any specific interpolation order.In one embodiment, by forming mixture and add this mixture in curable compound, form dispersion in conjunction with thickener and water.Perhaps, can form dispersion by any method known in the art.
This method also comprises the step of electrostatic spinning dispersion.In one embodiment, this step reduces the content of liquid (for example water), so that the compound of condensation curable solidifies.Be bound by under the situation of any particular theory not planning, think electrostatic spinning cause liquid for example water to small part evaporate, the compound of condensation curable solidifies as a result.The loss of solvent can allow curable compound blend, i.e. closely contact, thus allow to solidify.Be subject under the situation of any particular theory not planning, think the electric field force adjustable functional group that in electrostatic spinning, uses, so that they contact more easily.Can carry out the electrostatic spinning step by any method known in the art.Typical electrospinning process comprises that the use electric charge forms fiber.Typically, will form the employed dispersion of fiber and load in the syringe, adopt syringe pump, drive dispersion, and form drop at the place, tip of syringe to syringe tip.Pump can be controlled and form the flow that the employed dispersion of fiber arrives spinneret.The employed dispersion of formation fiber can have influence to the formation of fiber by the flow of syringe tip.Dispersion can be the about 0.5ml/min ml/min of about 0.005ml/min-by the flow at the tip of syringe, typically about 0.005ml/min-about 0.1, about 0.1ml/min of more typically about 0.01ml/min-and the about 0.1ml/min of the most about 0.02ml/min-.In a specific embodiment, dispersion can be about 0.05ml/min by the flow of syringe tip.
Then, typically drop is exposed under the high-tension electric field.Under the situation that does not have high voltage electric field, drop leaves the tip of syringe with 1/4 spherical form, and this is the result of drop inner surface tension force.Applying electric field causes sphere to be deformed into taper.The explanation that this distortion of droplet profile is accepted usually is that the surface tension in drop is neutralized by electric field force.The narrow diameter jet of dispersion flows out from cone is most advanced and sophisticated.Under some process conditions, the jet of dispersion experience " (whipping) twists thread " unstability phenomenon.This unstability that twists thread causes jet bifurcated repeatedly, thereby obtains network of fibers.Finally on collector plate, collect fiber.Think that in the electrostatic spinning process process liquid is water rapid evaporation from dispersion for example, stays the solid portion in the dispersion, form fiber and solidify this curable compound.Typically by solid conductive material, such as but not limited to aluminium, steel, nickel alloy, silicon chip,
Figure BDA0000055051390000141
Fabric, and cellulose (for example paper) forms collector plate.In the process of electrostatic spinning dispersion, collector plate plays the effect of electric current by the ground connection source of fiber.Along with time lapse, the fiber number of collecting on collector plate increases, and forms non-woven fibre mat on collector plate.Perhaps, replace using collecting board, can collect fiber on liquid surface, described liquid is not the part of dispersion, thereby realizes the self-supporting non-woven mat.An example collecting the spendable liquid of fiber is a water.
In various embodiments, the electrostatic spinning step comprises supply from the DC electric organ with about 100 kilovolts of (KV) generating capacities of about 10-.Especially, syringe is electrically connected on the electric organ.Drop is exposed to step under the high voltage electric field typically to be comprised and applies voltage and current to syringe.The voltage that is applied can be the about 100KV of about 5KV-, the about 40KV of typically about 10KV-, the about 35KV of more typically about 15KV-, the about 30KV of the most about 20KV-.In a concrete example, the voltage that is applied can be about 30KV.The electric current that is applied can be that about 0.01nA-is about 100,000nA, the about 1000nA of typically about 10nA-, the about 500nA of more typically about 50nA-, the about 100nA of the most about 75nA-.In a specific embodiment, electric current is about 85nA.Typically, when electrostatic spinning, dispersion 60 ℃ of environment temperature with interior temperature under.More typically, when electrostatic spinning, dispersion 60 ℃ of processing temperature with interior temperature under.
Think the compound of the partly solidified at least condensation curable of step of electrostatic spinning.In one embodiment, the step of electrostatic spinning is solidified the compound of condensation curable fully.In other embodiments, the step of electrostatic spinning do not solidify fully or even partly solidified curable compound, the result needs extra curing schedule.This method can comprise drying steps, with the compound of cure curable more fully.When curable compound is further defined as the compound of condensation curable, think that drying steps removes liquid (for example water) and drive condensation reaction to the right, promptly towards finishing.
This method also can comprise the step of the compound of aforesaid cure curable.Can be independent of electrostatic spinning step or combination with it, implement curing schedule.This step can comprise any curing schedule known in the art, comprising but be not limited to relate to radically curing, hydrosilylation cure, condensation cured, the UV photocuring, microwave curing, heat cure, and the combination those.
This method also can comprise the step that makes fiber annealing.Can finish this step by any method known in the art.In one embodiment, can use annealing steps to improve the hydrophobicity of fiber.In another embodiment, annealing steps can improve the rule degree of fiber microfacies.Annealing steps can comprise heating product.Typically, in order to carry out annealing steps, heating product is to the temperature higher than about 20 ℃ environment temperature.More typically, heating product is to about 40 ℃-Yue 400 ℃ temperature, more typically about 40 ℃-Yue 200 ℃.Heating product can cause the fusion of the increase of fiber contact in goods, produces chemistry or physical bond (being commonly referred to " crosslinked ") in fiber, makes one or more component volatilizations in the fiber, and/or the variation of fiber surface pattern.
Embodiment
The method according to this invention forms a series of fiber and non-woven mat (being goods of the present invention).Non-woven mat comprises by containing the fiber that the dispersion of silicone elastomer as the compound of condensation curable forms.
More specifically, the aqueous solution of 2g 2.5% poly(ethylene oxide) (2,000,000 number-average molecular weight) being joined 10g contains in the dispersion of 63wt%Dow Corning 84 Additive in water.Dow Corning Additive 84 comprises silica and contains the mixture of the crosslinked silicon rubber that can experience condensation cured functional group.Stir poly(ethylene oxide) and dispersion, form translucent white dispersion.In the preparation of electrostatic spinning, send dispersion in the stainless steel tube of 0.040 inch of internal diameter then by syringe/syringe pump.Between the aluminium foil of stainless steel tube and a slice ground connection, apply electric field.When applying electric field, the drop of locating at the tip of stainless steel tube is become thin white fiber by electrostatic spinning, and described white fiber is deposited on the aluminium foil of ground connection.In the sheet separation of 30cm, stretch out at the tip of 3cm, under the flow that applies voltage and 1ml/h of 22kV, carries out the electrostatic spinning step, carried out electrostatic spinning 1 hour.The gained fibre diameter is the 1-5 micron and tends to have fiber-fiber contact.As shown in Figure 1, in fiber, there is ball defects.
After electrostatic spinning 1 hour, fiber forms the about 200 microns opaque white color film of thickness.After 24 hours, from aluminium foil, peel off film and use the AllianceRT/5 Tensile Tester test that is available commercially from RTS, with the tensile property (stress/strain) that is determined at the breakaway poing place.More specifically, under the draw rate of 100mm/min, at the maximum load pond of 10N build-in test width the sample of " dog bone " shape of 0.1 inch film.Also generate load-deformation curve.The peak stress measured value of fiber is that about 19psi and strain measurement value are about 120%.In addition, load-deformation curve is roughly straight line, thereby shows that at breakaway poing place fiber be flexible.
The fiber of Xing Chenging shows in the aforementioned embodiment, and the electrostatic spinning dispersion allows to form opposite with continuous phase, demonstrates the fiber of decentralized photo (being the compound of condensation curable) feature.The fiber that forms in this embodiment demonstrates elastic stress and strain property, and elastic stress-strain curve.Form this fibrid and allow more effectively and accurately to produce the various materials that in medical science, science and process industry, use.Use dispersion also to allow to use all kinds of curable compounds, thereby form new product.For example using continuous phase wherein is that the dispersion of water allows to carry out electrostatic spinning process by evaporating harmless volatile liquid.In continuous phase, use active material for example bacterium can allow to be created on biological functionalized fiber curable in the one-step technology.
Describe the present invention and be appreciated that it is the wording character rather than the restriction of explanation that employed term is planned in illustrative mode.Obviously, in view of above-mentioned instruction, many modifications of the present invention and variation are possible and can put into practice the present invention beyond describing particularly.

Claims (50)

1. method of making goods, described goods comprise the fiber that is formed by dispersion, described method comprises the steps:
A. form and contain following dispersion:
(i) liquid and
(ii) the compound of condensation curable and
B. this dispersion of electrostatic spinning reduces the content of liquid, so that the compound of condensation curable is by condensation cured.
2. the process of claim 1 wherein that dispersion further comprises surfactant.
3. the method for claim 2 wherein before forming dispersion, combines surfactant with liquid.
4. the method for claim 2, wherein based on the weight of the compound of condensation curable, the amount of surfactant in dispersion is 0.5-5wt%.
5. the process of claim 1 wherein that dispersion further comprises thickener.
6. the method for claim 5, wherein thickener is further defined as poly(ethylene oxide).
7. the method for claim 5 wherein before forming dispersion, combines thickener with liquid.
8. the method for claim 5, wherein based on the weight of dispersion, the amount of thickener in dispersion is 0.05-5wt%.
9. the method for aforementioned any one claim, wherein the compound of condensation curable is selected from silane, siloxanes, silazane, silicone, silica, silene, silsesquioxane, and combination.
10. any one method of claim 1-8, wherein the compound of condensation curable is further defined as the silicon rubber of condensation curable.
11. any one method of claim 1-8, wherein the compound of condensation curable is further defined as the organic compound of condensation curable.
12. the method for claim 11, wherein the organic compound of condensation curable solidifies, form and be selected from polyester, nylon, polyurethane, epoxy resin, and the compound of combination.
13. any one method of claim 1-8, wherein the compound of condensation curable is further defined as the organic compound that silicon rubber and dispersion further comprise condensation curable.
14. any one method of claim 1-8, wherein dispersion comprises the compound that the 20-80 weight portion is curable, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
15. the method for claim 14, wherein dispersion comprises 20-80 weight portion liquid, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
16. any one method of claim 1-8, wherein liquid is further defined as water.
17. the method for claim 16, wherein the compound of condensation curable is dispersed in the water.
18. any one method of claim 1-8 further comprises dried fibres, with the content of further reduction liquid so that the compound step of curing of condensation curable.
19. the process of claim 1 wherein that dispersion comprises the decentralized photo of the compound that contains condensation curable and contains the continuous phase of liquid, surfactant and thickener.
20. any one method of claim 1-8, wherein the stress of fiber is for 15psi and strain are at least 100% at least.
21. a fibre, it comprises the compound of curing and contains following dispersion by electrostatic spinning and forms:
A. liquid; With
B. the compound of condensation curable;
Wherein reduce the content of described liquid, so that the compound of described condensation curable solidifies.
22. the goods of claim 21, wherein said dispersion further comprises surfactant.
23. the goods of claim 22 are wherein before forming described dispersion, in conjunction with described surfactant and described liquid.
24. the goods of claim 22, wherein based on the weight of the compound of described condensation curable, the amount of described surfactant in described dispersion is 0.5-5wt%.
25. the goods of claim 21, wherein said dispersion further comprises thickener.
26. the goods of claim 25, wherein said thickener is further defined as poly(ethylene oxide).
27. the goods of claim 25 are wherein before forming described dispersion, in conjunction with described thickener and described liquid.
28. the goods of claim 25, wherein based on the weight of described dispersion, the amount of described thickener in described dispersion is 0.05-5wt%.
29. any one goods of claim 21-28, the compound of wherein said condensation curable is selected from silane, siloxanes, silazane class, silicone, silica, silene, silsesquioxane, and combination.
30. any one goods of claim 21-28, the compound of wherein said condensation curable is further defined as silicon rubber.
31. any one goods of claim 21-28, the compound of wherein said condensation curable is further defined as the organic compound of condensation curable.
32. the goods of claim 31, the organic compound of wherein said condensation curable is selected from polyester, nylon, polyurethane, epoxy resin, and combination.
33. any one goods of claim 21-28, the compound of wherein said condensation curable are further defined as the organic compound that silicon rubber and described dispersion further comprise condensation curable.
34. any one goods of claim 21-28, wherein said dispersion comprises the described curable compound of 20-80 weight portion, with respect to the described dispersion meter of 100 weight portions, as long as the total amount of described dispersion is no more than 100 weight portions.
35. the goods of claim 34, wherein said dispersion comprise the described liquid of 20-80 weight portion, with respect to the described dispersion meter of 100 weight portions, as long as the total amount of described dispersion is no more than 100 weight portions.
36. any one goods of claim 21-28, wherein said liquid is further defined as water.
37. the goods of claim 21, wherein said dispersion comprise the decentralized photo of the compound that contains described condensation curable and contain the continuous phase of described liquid, surfactant and thickener.
38. the goods of claim 37, the compound of wherein said condensation curable comprises that with respect to the described dispersion meter of 100 weight portions amount be the silicone elastomer of 20-80 weight portion, described liquid is further defined as water and is the 20-80 weight portion with respect to 100 weight portion dispersion meter amounts, described surfactant comprises that with respect to the described dispersion meter of 100 weight portions amount be the methyl aminomethyl propanol of 0.5-5 weight portion, and described thickener is further defined as poly(ethylene oxide) and is the 0.05-5 weight portion with respect to the described dispersion meter of 100 weight portions amount.
39. any one goods of claim 21-28, it is further defined as non-woven mat.
40. a method of making goods, described goods comprise the fiber that is formed by dispersion, and described method comprises the steps:
A. form and contain following dispersion:
(i) liquid and
(ii) curable compound,
B. the electrostatic spinning dispersion forms fiber; With
C. solidify this curable compound.
41. the method for claim 40, wherein dispersion further comprises surfactant and thickener.
42. the method for claim 41, wherein based on the weight of curable compound, the amount of surfactant in dispersion is 0.5-5wt%.
43. the method for claim 41, wherein thickener is further defined as poly(ethylene oxide).
44. the method for claim 41, wherein the amount of thickener in dispersion is the 0.05-5% of dispersion weight.
45. any one method of claim 40-44, wherein curable compound is selected from silane, siloxanes, silazane, silicone, silica, silene, silsesquioxane, and combination.
46. any one method of claim 40-44, wherein curable compound is further defined as silicon rubber.
47. any one method of claim 40-44, wherein curable compound is further defined as the curable organic compound.
48. any one method of claim 40-44, wherein dispersion comprises 20-80 weight portion liquid, with respect to 100 weight portion dispersion meters, as long as the total amount of dispersion is no more than 100 weight portions.
49. any one method of claim 40-44, wherein liquid is further defined as water.
50. the method for claim 49, wherein curable compound is dispersed in the water.
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EP2318575A2 (en) 2011-05-11
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US20110165811A1 (en) 2011-07-07
CA2735440A1 (en) 2010-03-04
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